Reactive dye compounds

ABSTRACT

New, highly multifunctional reactive dye compounds are provided. The number of leaving groups in the non-chromophoric part of the molecule added to the number of chromophore moieties is at least equal to 5, preferably in the range of from 5 to 12, more preferably from 5 to 6. The new reactive dye compounds preferably have at least two asymmetric bridges.

TECHNICAL FIELD

[0001] The present invention relates to reactive dye compounds. Inparticular the present invention relates to reactive dye compoundscomprising at least one chromophoric moiety D and at least one leavinggroup Y. The sum of the number of chromophoric moiety or moieties D andthe number of leaving group or groups Y is at least equal to 5.

BACKGROUND OF THE INVENTION

[0002] Reactive dye compounds are known in the art for dyeing varioussubstrates. Such substrates include for example proteinaceous materialssuch as keratin, e.g. found in hair, skin and nails and various animalbody parts such as horns, hooves and feathers, and other naturallyoccurring protein containing materials, e.g. silk and saccharide-derivedmaterials such as those derived from cellulose or cellulose derivatives,e.g. natural products such as cotton, and synthetic fibres such aspolyamides.

[0003] Examples of classes of such reactive dyes which are well known inthe art include dyes containing a mono- or dichloro- or fluoro-1,3,5-triazinyl group, trichloro-pyrimidyl or mono-chloro-difluoropyrimidyl group, alpha,beta-dihalogen-propionyl group,beta-halogenoethyl-sulphonyl group, beta-halogenoethylsulphamyl group,chloroacetyl amino, beta-(chloro-methyl)-beta-sulphatoethylsulphamylgroup, or a vinyl sulphonyl, 2,4-dinitro-3,5-difluoroaryl group.

[0004] In the case of the dyes containing a triazinyl group or apyrimidyl group, in place of the reactive halogen atoms one can useother groups which dissociate on reaction with a nucleophile (leavinggroups). Canadian Patent 771632, for example, discloses examples of suchother groups including sulphonic acid, thiocyanate, sulphophenoxy,sulphophenyl thio, nitrosulphophenoxy groups, and quaternary ammoniumgroups.

[0005] Dyes and Pigments 14, 1990, pages 239-263, “Synthesis andApplication of Reactive Dyes with Heterocyclic Reactive Systems”discloses fibre reactive dyes containing monochloroordichloro-pyrimidine heterocycle with quaternary ammonium substituents.

[0006] There are many different types of reactive dyes for dyeingcellulosic and polyamide-type substrates described in the art.WO9951684, Lewis et al., incorporated herein by reference, disclosesreactive dyes comprising a) at least one chromophore moiety, b) at leastone nitrogen-containing heterocycle, c) a linking group to link eachchromophore moiety to each nitrogen-containing heterocycle characterisedin that at least one nitrogen-containing heterocycle is substituted withat least one thio-derivative and at least one quaternized nitrogenderivative. These reactive dyes exhibit increased values of Exhaustion(E) and Fixation (F) compared to previous reactive dyes. A highExhaustion value for a particular dye compound means that a low level ofspent dye remains in the effluent after the dyeing process is complete.The Fixation Value (F) of a reactive dye compound is a measure of theextent of covalent bonding with the substrate based on the dyeoriginally absorbed during the dyeing process.

[0007] In addition to these properties, it is also important that thereactive dyes perform well once they have been applied to the textile.The industrial tests commonly used to assess the performance of dyedtextiles measure their light fastness, wet and dry crock resistance,dye-transfer staining behavior and wash fastness. In the light fastnesstest, dyed samples are placed in a sunlight-mimicking unit andirradiated for set amounts of time. The stain test is carried out byattaching to a sample a multifiber test strip. The swatches are run inconsumer-mimicking conditions in a washing machine. The test is designedto evaluate any cross staining propensity of dye that might be removedin washing to stain other fibers. The wash fastness test measures thecolor change on the fabric from the original shade. The sample is washedunder consumer-mimicking conditions in a washing machine and theassessment is done visually by a trained (experienced) technician.

SUMMARY OF THE INVENTION

[0008] According to the present invention there is provided reactive dyecompounds comprising at least one chromophoric moiety D and at least oneleaving group Y, wherein the sum of the number of chromophoric moiety ormoieties D and the number of leaving group or groups Y is at least equalto 5, preferably in the range of from 5 to 12, more preferably from 5 to6.

[0009] According to the present inventions there is also provided newreactive dye compounds having at least two asymmetric bridging moieties.The asymmetric bridging moieties are preferably dissymmetric, and aremore preferably selected from the group consisting of cysteamine,cysteine and derivatives thereof, even more preferably from the groupconsisting of cysteamine and cysteine.

[0010] The preferred class of compounds according to the presentinvention has the general formula (I):

[0011] The precise meaning of D, L, B, Z and G1 is disclosed in thedetailed description section below.

[0012] The compounds of the present invention exhibit excellentExhaustion (E) and Fixation (F) values and also provide good results interms of light fastness, wet and dry crock resistance, perspiration,dye-transfer staining and wash fastness. In addition, the compounds ofthe present invention provide significantly more intense dyeing, i.e.greater colour intensity in the dyed substrate than comparative dyeingswith commercially available reactive dyes applied at equivalent depth ofshades.

DETAILED DESCRIPTION OF THE INVENTION

[0013] As used herein the term “reactive dye” means a dye containing oneor more reactive groups capable of forming covalent bonds with thesubstrate to be dyed, or a dye that forms such a reactive group in situ.

[0014] Preferred compounds according to the present invention have thefollowing formula (I)

[0015] The precise meaning of D, L, B, Z and G1 is disclosed below.

[0016] Chromophore Moiety (D)

[0017] The reactive dye compounds herein can comprise one or morechromophore moieties D. In reactive dye compounds comprising two or morechromophore moieties these can be the same or different. Preferably thereactive dye compounds herein comprise from one to six chromophoremoieties, more preferably from one to three chromophore moieties. Anychromophore moieties suitable for use for dyeing substrates can be usedin the present invention. The term chromophore as used herein means anyphotoactive compound and includes any coloured or non-coloured lightabsorbing species, e.g. fluorescent brighteners, UV absorbers, IRabsorbing dyes. The term chromophore as used herein also includesorganic radical such as β-sulphatoethylsulphonyl benzene, vinylsulphonyl benzene, chloroethylsulphonyl benzene, β-S-thiosulphatoethylsulphonyl benzene, di(aminoethylsulphonyl) benzene provided that thereactive dye compound contains at least one other chromophore group.

[0018] Suitable chromophore moieties for use in the dye compounds hereininclude the radicals of monoazo, diazo or polyazo dyes, or heavy metalcomplex azo dyes derived therefrom, anthraquinone, phthalocyanine,formazan, azomethine, dioxazine, phenazine, stilbene, triphenylmethane,xanthene, thioxanthene, nitroaryl, naphthoquinone, pyrenequinone orperylenetetracarbimide dyes.

[0019] Other suitable chromophore moieties for use in the dye compoundsherein include those disclosed in EP-A-0,735,107 (Ciba-Geigy),incorporated herein by reference, including the radicals describedtherein which contain substituents customary for organic dyes, such assulphonate substituents which enhance the water-soluble properties ofthe dye compound.

[0020] Examples of chromophore D moieties for use herein arepolysulphonated azo chromophores such as those present in Procion™ dyescommercially available from BASF. Typical chromophores D are exemplifiedby those in Procion™ Red MX-8B, Procion™ Yellow MX-8G, Procion™ YellowMX-3R and Procion™ Blue MX-2G.

[0021] Conveniently the chromophoric part may be represented as D, thusthese dyes can be represented by:

[0022] Other suitable chromophores are present in Drimalan™ andDrimarene™ dyes commercially available from Clariant and Levafix™ dyescommercially available from DyStar.

[0023] Linking Moiety (L)

[0024] The preferred compounds herein further comprise a linking moietyL that links each multi-bonding moiety Z (such as nitrogen-containingheterocycles) to each chromophore moiety D. Any linking moiety suitablefor use in dyeing substrates can be used in the present invention.

[0025] Preferably the linking moiety is selected from the groupconsisting of —NR—, —C(O)NR—, NRSO₂, —(CH₂)_(k)— and —SO₂—(CH₂)_(k)—wherein R is H or C₁-C₄ alkyl which can be substituted by halogen,preferably fluorine or chlorine, hydroxyl, cyano, C₁-C₄ alkoxy, C₂-C₅alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato and wherein k isan integer with a value between 1 and 4. When the linking moiety isdissymmetric (such as —C(O)NR—, —NRSO₂—), the D and Z moieties can belinked to any side of the linking moiety. When Z is a triazine orpyrimidine, a preferred linking moiety is NR, preferably where R is H orC₁-C₄ alkyl, more preferably where R is H or CH₃, especially H. When Zis quinoxaline or phthalazine, a preferred linking moiety is —NR(C═O)—,where R is H or C1 —C4 alkyl, more preferably where R is H or CH₃,especially H.

[0026] Multi-Bonding Moiety Z

[0027] The multi-bonding moieties Z are functionally defined as moietiesforming covalent bonds with at least 3 other moieties. In formula (I) to(IX) described below, these other moieties are selected from the groupconsisting of the linking moiety L defined above, bridging moiety B andmoiety G1, which are defined hereafter. The exact nature of the moietiesto which the Z moiety bonds depends on the position of the moiety Zinside the reactive-dye molecule as described in the general formula (I)or in the other preferred formula (II) to (IX). The number ofmulti-bonding moieties Z in the reactive dyes of formula (II) to (IX) ofthe present invention is at least 2, and for the reactive dyes offormula (I) it is at least three (the reactive dye compounds of formula(I) comprise at least one group G2, defined below).

[0028] In one reactive dye molecule, if there is two or moremulti-bonding moieties Z these can be the same or different.

[0029] Preferred Z moieties are selected from the group consisting ofnitrogen (N),

[0030] and aromatic compounds. Especially preferred are aromaticN-heterocycles and aromatic compounds activated by electron withdrawinggroups.

[0031] When Z is

[0032] there is no preference to which carbon atom (primary orsecondary) the other moieties (e.g. L, B and G1) are connected.

[0033] Preferably, the Z moieties herein comprise at least one aromaticcompound. More preferably all Z moieties are selected from aromaticcompounds, especially nitrogen containing heterocycles. Suitablenitrogen containing heterocycles for use herein include monocyclic,bicyclic or polycyclic, unsaturated heterocycles containing at least onenitrogen heteroatom. When monocyclic rings are used, they are preferablyselected from unsaturated rings having from about 3 to about 7 ringatoms, especially 5 or 6 ring atoms, comprising from about 1 to about 3nitrogen heteroatoms, preferably 2 or 3 nitrogen heteroatoms. Whenbicyclic heterocycles are used, they preferably comprise an unsaturatednitrogen containing heterocycle having 3 to 7 ring atoms, preferably anunsaturated nitrogen containing heterocycle having 5 or 6 ring atomscomprising 1 or 2 nitrogen atoms, fused to a 5 to 7 membered carbocyclepreferably a 6-membered unsaturated carbocycle. When bicyclicheterocycles are used, the other moieties (e.g. L, B and G1) arepreferably attached to the nitrogen containing heterocyclic ring.

[0034] Preferred for use herein are 5 or 6 membered unsaturated nitrogencontaining monocyclic heterocyclic rings comprising 2 or 3 nitrogenheteroatoms or bicyclic rings containing a 5 or 6 membered unsaturatedheterocyclic ring containing 2 nitrogen heteroatom fused to a 6 memberedunsaturated carbocycle.

[0035] Examples of suitable heterocycles for use herein include, but arenot necessarily limited to triazine, pyrimidine, quinoxaline,pyrimidinone, phthalazine, pyridazone and pyrazine. Preferred for use inthe compounds herein are triazine, pyrimidine and quinoxaline.

[0036] Aromatic compounds activated by electron withdrawing groups suchas NO, NO₂, CN, CHO, SO₂Me, NMe³⁺, CF₃, COOH, COO—C1-C4 alkyl, SO₃ ⁻,preferably NO or NO₂, are also suitable. An example of a suitableactivated benzene ring is

[0037] In addition to the bonding to L, B and G1, a Z moiety can beoptionally bonded to other moieties such as one or more leaving group Ydefined below.

[0038] Leaving Group Y

[0039] The reactive dyes of the present invention comprise at least oneleaving group Y. The function of the leaving group Y is to besubstituted during the dyeing process by a substituting nucleophilicgroup on the surface of the substrate. The covalent bond formed afterthe substitution accounts for the stability of the color on thesubstrate after the dyeing process is completed. Therefore reactive dyespreferably contain more than one leaving group. In the case ofcellulosic fibers, the substitution process is usually carried out inalkaline condition (pH>8) in order to generate a sufficientconcentration of nucleophilic cellulosate anions.

[0040] All groups capable of being substituted in the condition of thedyeing process are suitable. Examples of leaving groups are —Cl, —Br,—F, —I, —SO₃H, —OSO₃H, —SSO₃H, —O—C₆H₄—SO₃H, —OCO—CH₃, —OPO₃H₂,—OCO—C₆H₅, —OSO₂—C₁-C₄ alkyl, —OSO₂—N(C₁-C₄ alkyl)₂,

[0041] and quaternized nitrogen derivatives.

[0042] Preferred leaving groups Y are selected from the group consistingof —Cl, —Br, —F and —OSO₃H, more preferably from the group consisting of—Cl and —F when Y is bonded to an N-containing heterocycle and —Br whenY is bonded to

[0043] Examples of suitable quaternized nitrogen derivatives aredescribed in WO99/51684, Brock et al. Particularly preferred quaternizednitrogen derivatives for use herein are nicotinate, diazabicyclooctane(DABCO), dimethylaminobetaine and isonicotinate, especially nicotinate.

[0044] In one reactive dye compound comprising more than one leavinggroup Y, these can be the same or different.

[0045] Group G1

[0046] G1 is selected from Y (leaving group as described above) and—B-G2. The function of G1 is to increase the multi-functionality of thereactive dye molecule by either providing a leaving group Y or a groupG2 that comprises a multi-bonding group Z. G2 is defined hereafter. Inreactive dye compounds comprising two or more groups G1, these can bethe same or different.

[0047] Group G2

[0048] G2 is selected from

[0049] The function of G2 is to increase the multi-functionality of thereactive dye compound by increasing the number of leaving groups Y orchromophore moieties D. In reactive dye compounds comprising two or moregroups G2, these can be the same or different.

[0050] Bridging Moiety B

[0051] The function of the bridging moieties B is to provide a junctionbetween two Z groups. The bridging moieties are preferably selected fromthe group consisting of

[0052] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H, and

[0053] wherein R″ is selected from the group consisting of H, C1-C4alkyl group and

[0054] —CR′₂—CR′₂—S-G2.

[0055] R′ and R″ can be the same or different inside a given bridgingmoiety.

[0056] Preferred bridging moieties are asymmetric, more preferablydissymmetric. Asymmetric as used herein means that the bridging moietycomprises at least two different functional groups that have reacted toform covalent bonds with other functional group. Dissymmetric as usedherein means that the bridging moiety comprises two different functionalgroups with different affinity for the Z moieties. Preferreddissymmetric bridging moieties are based on cysteamine or cysteine andhave the formula:

[0057] wherein R′ and R″ are as defined above. Even more preferredbridging moieties are cysteamine or cysteine:

[0058] —S—CH₂—CH₂—NH—

[0059] cysteamine

[0060] —S—CH₂—CH(COOH)—NH—

[0061] cysteine

[0062] It has now been found that asymmetric, preferably dissymmetric,bridging moieties allow a better control of the synthesis of reactivedye molecules. By choosing parameters such as the reaction temperatureand pH, it is possible to control the number and the way bridgingmoieties attach to other moieties such as a multi-bonding moiety Z. Itcan also be controlled by what end (the sulphur or the nitrogen end inthe case of cysteamine or cysteine) they will bond to a particular Zmoiety.

[0063] In reactive dye compounds comprising two or more bridgingmoieties B, these can be the same or different.

[0064] Following formula (II) to (VI) below represent variousembodiments of preferred reactive dyes according to formula (I) definedabove.

[0065] Formula (VII), (VIII) and (IX) represent other preferred reactivedye compounds according to the present invention.

[0066] Preferred Reactive Dyes Having the Formula (II) Below:

[0067] wherein

[0068] D is as defined in formula (I) above;

[0069] L is as defined in formula (I) above;

[0070] Z is as defined in formula (I) above;

[0071] Y is as defined in formula (I) above;

[0072] B is

[0073] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H; and

[0074] R″ is selected from the group consisting of H and C1-C4 alkylgroup,

[0075] B preferably being —NH—CH₂—CH₂—S— or —NH—CHCOOH—CH₂—S—;

[0076] wherein when there is more than one D, L, Z, Y. R, R′, R″ or Bgroup these are not necessarily the same;

[0077] and salts and esters thereof.

[0078] Preferred Reactive Dyes Having the Formula (III) Below:

[0079] wherein

[0080] D is as defined in formula (I) above;

[0081] L is as defined in formula (I) above;

[0082] Z is as defined in formula (I) above;

[0083] Y is as defined in formula (I) above;

[0084] G1 is as defined in formula (I) above;

[0085] G2 is as defined in formula (I) above;

[0086] B is

[0087] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H; and

[0088] R″ is selected from the group consisting of H and C1-C4 alkylgroup,

[0089] B preferably being —NH—CH₂—CH₂—S— or —NH—CHCOOH—CH₂—S—;

[0090] wherein when there is more than one D, R, R′, R″, L, Z, Y, G1, G2or B group these are not necessarily the same; and

[0091] wherein the reactive dye compound comprises at least one groupG2;

[0092] and salts and esters thereof.

[0093] Preferred Reactive Dyes Having the Formula (IV) Below:

[0094] wherein

[0095] D is as defined in formula (I) above;

[0096] L is as defined in formula (I) above;

[0097] Z is as defined in formula (I) above;

[0098] Y is as defined in formula (I) above;

[0099] G1 is as defined in Formula (I) above;

[0100] G2 is as defined in Formula (I) above;

[0101] B is as defined in Formula (I) above;

[0102] wherein at least one, and preferably all, B is S—,

[0103] wherein when there is more than one B, D, R, L, Z, Y, G1 or G2within the same molecule these are not necessarily the same; and

[0104] wherein the reactive dye compound comprises at least one groupG2;

[0105] and salts and esters thereof.

[0106] Preferred Reactive Dyes Having the Formula (V) Below:

[0107] wherein

[0108] D is as defined in formula (I) above;

[0109] L is as defined in formula (I) above;

[0110] Z is as defined in formula (I) above;

[0111] Y is as defined in formula (I) above;

[0112] G1 is as defined in Formula (I) above;

[0113] G2 is as defined in Formula (I) above;

[0114] B is a bridging group selected from the group consisting of

[0115] wherein R″ is selected from the group consisting of H, C1-C4alkyl group and

[0116] —CR′₂—CR′₂—S— G2; and

[0117] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H,

[0118] wherein when there is more than one D, R, R′, R″, L, Z. Y, G1,G2, or B group these are not necessarily the same; and

[0119] wherein the reactive dye compound comprises at least one bridginggroup B wherein R″ is —CR′₂—CR′₂—S-G2

[0120] and salts and esters thereof.

[0121] Preferred Reactive Dyes Having the Formula (VI) Below:

[0122] wherein

[0123] D is as defined in formula (I) above;

[0124] L is as defined in formula (I) above;

[0125] Z is as defined in formula (I) above

[0126] Y as defined in formula (I) above

[0127] G1 is as defined in Formula (I) above;

[0128] G2 is as defined in Formula (I) above;

[0129] B is a bridging moiety, preferably selected from the groupconsisting of

[0130] wherein R″ is selected from the group consisting of H, C1-C4alkyl group and

[0131] —CR′₂—CR′₂—S— G

[0132] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H,

[0133] B preferably being —NH—CH₂—CH₂—S— or —NH —CHCOOH—CH₂—S−;

[0134] wherein when there is more than one D, R, R′, R″, L, Z, Y, G1, G2or B group these are not necessarily the same;

[0135] and salts and esters thereof.

[0136] Other Preferred Reactive Dyes According to the Present Inventionhave the Formula (VII) Below:

[0137] wherein

[0138] D is as defined in formula (I) above;

[0139] L is as defined in formula (I) above;

[0140] Z is as defined in formula (I) above;

[0141] Y is as defined in formula (I) above

[0142] B is selected from the group consisting of

[0143] wherein R″ is selected from the group consisting of H and C1—C4alkyl group; and

[0144] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H;

[0145] B preferably being NH CH₂—CH₂—S— or —NH—CHCOOH—CH₂—S—

[0146] wherein each of R, R′, R″, L, Z, Y, or B are not necessarily thesame;

[0147] and salts and esters thereof.

[0148] Other Preferred Reactive Dyes According to the Present Inventionhave the Formula (VIII):

[0149] wherein

[0150] D is as defined in formula (I) above;

[0151] Z is as defined in formula (I) above;

[0152] Y is as defined in formula (I) above

[0153] R is selected from the group consisting of H, C₁-C₁₀ alkyl group,C₁-C₁₀ carboxylic acid and sulphonate, preferably H and COOH, morepreferably H;

[0154] wherein each of D, R, Z and Y are not necessarily the same;

[0155] and salts and esters thereof.

[0156] Other Preferred Reactive Dyes According to the Present Inventionhave the Formula (IX):

[0157] wherein

[0158] D is as defined in formula (I) above;

[0159] Z is as defined in formula (I) above;

[0160] Y is as defined in formula (I) above;

[0161] R is selected from the group consisting of H, C1-C₁₀ alkyl group,C1-C₁₀ carboxylic acid and sulphonate, preferably H and COOH, morepreferably H;

[0162] wherein each of Z or Y are not necessarily the same;

[0163] and salts and esters thereof.

[0164] Method of Preparation

[0165] The present invention furthermore relates to processes for thepreparation of the dyes herein. In general, reactive dye compoundsaccording to the present invention such as those having the generalformula (I) to (IX) can be prepared by reacting suitable precursors withone another, at least one of which contains a group D-L-Z, wherein D, Land Z are as defined above. Various methods of preparations as well asdifferent reactive dye molecules will be exemplified hereafter. Theperson skilled in the art can easily apply the following generalreactions and the specific reactions exemplified to synthesize thedifferent dyes covered by the present invention and in particularaccording to formula (I) to (IX) but not specifically exemplified.

[0166] One method for synthesizing reactive dyes according to thepresent invention using a starting reactive dye compound and bridgingmoiety B comprises the steps of:

[0167] a) reacting said starting dye compound with said bridging group Band forming one bond, and

[0168] b) reacting the second moiety of said bridging group B with amoiety Z.

[0169] B is preferably dissymmetric and more preferably has thefollowing formula:

[0170] wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H; and R″is selected from the group consisting of H and C₁-C₄ alkyl group.

[0171] More preferably at least one R′ is COOH.

[0172] Steps a) and/or step b) are preferably repeated at least twice.

[0173] Synthesis of Reactive Dyes According to Formula (II)

[0174] A general 2-steps synthesis route for these compounds isillustrated in Diagram 1 below. The starting material is a chromophoredye linked to a multi-bonding moiety Z comprising at least 2 leavinggroups such as chlorine. These starting materials are commerciallyavailable or can be easily synthesized by the person skilled in the art.The first step of the reaction consists of the substitution of the twoleaving groups by two bridging groups such as cysteamine. The secondstep of the reaction consists of the substitution of a Z multi-bondingmoiety on the unreacted side of the two bridging moieties.

[0175] Alternatively, it would be obvious for the person skilled in theart that the dissymmetric bridging moiety can be first reacted with themulti-bonding Z moiety. The mercapto (—SH) moiety is more reactive thanthe amino (—NH₂) moiety, therefore this will lead to a final reactivedye wherein the starting reactive dye is linked to the amino moiety ofthe bridging group instead of its mercapto moiety.

[0176] SYNTHESIS of Reactive Dyes According to Formula (III)

[0177] A general 2-step synthesis route for these compounds isillustrated in Diagram 2 below. The starting material is a chromophoredye linked to a multi-bonding moiety Z comprising at least 2 leavinggroups such as chlorine. These starting materials are commerciallyavailable or can be easily synthesized by the person skilled in the art.The first step of the reaction consists of the substitution of one ofthe leaving group by an asymmetric or dissymmetric bridging moiety Bsuch as cysteamine. To avoid multi-substitution, the starting reactivedye and the bridging moiety B should be introduced in equimolar quantityand the temperature of the reaction sufficiently low. In the secondstep, two moles of the intermediates obtained after the first step arereacted with one mole of a Z multi-bonding moiety to give the finalreactive dye. The reactive dyes according to formula (III) have at least2 chromophore dye moieties and this synthesis can be easily adapted toobtain reactive dyes with two different chromophores by reacting themulti-bonding Z moiety to intermediates with different dye chromophoresas is exposed in the following diagram.

[0178] Alternatively, the asymmetric bridging moiety B can be firstreacted with the multi-bonding Z moiety. In the case of cysteamine, themercapto (—SH) moiety is more reactive than the amino (—NH₂) moiety. Inthe final reactive dye, the starting reactive dye is therefore linked tothe amino moiety of the bridging moiety instead of its mercapto moiety.

[0179] When all Starting Reactive Dyes are the same:

[0180] A third group (3) can be substituted on the Z′ group to give amolecule comprising 3 dye moieties.

[0181] When the Starting Reactive Dyes are Different:

[0182] The first step is repeated once for each different startingreactive dye. They are subsequently substituted on the Z′ moiety. Withtwo different starting reactive dyes, the final compound is:

[0183] As usual, inside one reactive dye compound each of L, Z, R′ and Ygroups can be the same or different.

EXAMPLES

[0184] The following examples serve to illustrate the compounds andcompositions of the present invention.

[0185] The starting compounds and components given in the examples aboveare usually used in form of their sodium salts. The starting reactivedye compounds can be purified by conventional means from thecommercially available reactive dyes mentioned in the examples below.

[0186] Examples 1, 2, 3, 4 and 5 exemplify reactive dye compoundsaccording to Formula (II).

[0187] Examples 6, 7 and 8 exemplify reactive dye compounds according toFormula (III).

[0188] Example 9 exemplifies reactive dye compounds according to Formula(IV).

[0189] Examples 10, 11 and 12 exemplify reactive dye compounds accordingto Formula (V).

[0190] Examples 13 and 14 exemplify reactive dye compounds according toFormula (VI).

[0191] Examples 15, 16, 17 and 18 exemplify reactive dye compoundsaccording to Formula (VII).

Example 1

[0192] Cysteamine hydrochloride (0.2 mol) was dissolved in water (150ml) and the pH of the solution adjusted to 7.5 with the addition ofsolid sodium carbonate at 20° C. To this solution was added slowly asolution of 0.1 mol of a dichloro-5-triazine dye, Procion™ Yellow MX-3Rdissolved in 300 ml water.

[0193] The nucleophilic substitution with the thiol started immediatelyresulting in the formation of compound 1(a). The liberated HCl wascontinuously neutralized by additions of sodium carbonate. After 5-8hours this first-stage reaction was complete as indicated bystabilisation of the pH. At this stage the bis-cysteamine dye 1(a) wasisolated by reducing the pH to 4; the solid dye was filtered off andwashed with a sodium sulphate solution (20% w/w) to remove unreactedcysteamine.

[0194] The above reaction is summarized in the diagram below:

[0195] Cyanuric chloride (0.2 mol) was dissolved in acetone (400 ml) andto this solution was added slowly, with good stirring, an aqueoussolution of 1(a) prepared above (0.1 mol of dye dissolved in 200 mlwater at pH 7.5-set with sodium carbonate). The temperature wasmaintained at 20° C. The reaction liberated hydrochloric acid and the pHwas therefore maintained at 7.5 by portion wise additions of solidsodium carbonate as required. After 6 hours the pH stabilized indicatingthat the reaction was complete. Sodium sulphate was added to thesolution to “salt out” the dye (1 b) which was filtered and dried in adessicator.

Example 2

[0196] The same procedure as in example 1 was followed except thatcysteine hydrochloride was used instead of cysteamine hydrochloride toproduce the dye (2 b) below:

[0197] The additional carboxylate groups present in the cysteine linkagemeans that the aqueous solubility of this dye is higher at pH valuesgreater than 4. The use of such dyes in pad-batch, pad-steam or pad-bakeprocesses requires high aqueous solubility (>80 g dm⁻³) and thus thecysteine crosslink would provide excellent dyes for this purpose.

Example 3

[0198] In this example a trichloropyrimidine dye, Drimarene™ YellowX-4RNA (Clariant) was used instead of the Procion™ MX dye as forexample 1. The same synthesis route was used only for the differencethat the temperature of the first stage of the reaction was 30° C.instead of 20° C. The following diagram summarizes the synthesis.

Example 4

[0199] In this example a 2,4-difluoro-5-chloro pyrimidine dye,Drimarene™ Golden Yellow K-2R (Clariant) was used as starting reactivedye.

Example 5

[0200] In this example, the starting reactive dye was an amidoquinoxaline dye. The starting material can be prepared by reacting acorresponding quinoxaline carbonyl halide with a dye comprising an aminogroup.

Example 6

[0201] Cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) (0.1 mol) wasdissolved in acetone (200 ml). A solution of cysteamine hydrochloride(0.3 mol in 100 ml water) was slowly added to this solution. The pH ofthe solution was maintained at 7-8 by the addition of solid sodiumcarbonate. After 7 hours at 20° C. the pH stabilized and compound (6a)precipitated.

[0202] Compound (6a) (0.1 mol) was dissolved in water (100 ml) bywarming to 30° C. at pH 6. 0.3 mol of Procion Yellow MX-3R dissolved in300 ml water was slowly added. The pH was maintained at 6-7 by theaddition of solid sodium carbonate. After 6 hours, the pH stabilizedindicating the formation of dye (6b).

[0203] The dye was “salted out” by the addition of sodium sulphate,filtered and washed with an almost saturated sodium sulphate aqueoussolution. The dye was dried in a dessicator.

Example 7

[0204] This example illustrates the synthesis of a reactive dyecomprising 3 dye chromophores. The starting material was adichlorotriazine reactive dye such as Procion™ Red MX-8B. In the firststage of the reaction, an aqueous solution comprising 3 moles ofcysteamine was slowly added to an aqueous solution of the starting dye(3 moles). In the second stage of the reaction 1 mole of cyanuricchloride dissolved in acetone was added. One third of the cyanuricchloride reacted at 0° C. When the pH stabilized, the temperature wasraised at 40° C. where the second third reacted. Finally the temperaturewas raised to about 80° C. and the last third reacted. The pH wasconstantly maintained at 7.5 by the addition of Na₂CO₃ to neutralize theproduction of HCl during the reaction.

Example 8

[0205] In this example, the starting material was a dichlorotriazinereactive dye (Procion™ Yellow MX-3R). In the first stage of thereaction, an aqueous solution comprising 2 moles of cysteamine wasslowly added to an aqueous solution of the starting dye (2 moles). Inthe second stage of the reaction 1 mole of cyanuric chloride dissolvedin acetone was added and the temperature kept at 0° C. until the pHstabilized. The temperature was then raised at 40° C. until the pHstabilized. The pH was constantly maintained at 7.5 by the addition ofNa₂CO₃ to neutralize the production of HCl during the reaction.

Example 9

[0206] This example illustrates the synthesis of a reactive dyeaccording to formula (IV). The starting material for this example was acommercially available 1,3,5-triazine-2,4,6-trithiol trisodium salt(available from Degussa). 3 moles of starting reactive dye (for exampleProcion™ Yellow MX-3R) were slowly added to an alkaline solution of 1mol trimercapto-5-triazine (pH 9, 40° C.). The pH was maintained at 9 byaddition of sodium carbonate. The stabilization of the pH indicated theend of the reaction.

Example 10

[0207] This example illustrates the synthesis of a reactive dyeaccording to formula (IV). The starting material was a commerciallyavailable N-(2-mercaptoethyl)cysteamine. In the first stage of thereaction, 2 mol of Procion™ Red MX-SB were added to an aqueous solutionof the dithiol at 20° C. The pH was maintained at 7.5 during thereaction by addition of Na₂CO₃. In the second stage of the reaction, onemole of cyanuric chloride (dissolved in acetone) was slowly added to theabove aqueous solution. The pH was maintained at 7.5 (by addition ofNa₂CO₃) and the temperature at 15° C.

Example 11

[0208] This example illustrates the synthesis of a reactive dyeaccording to formula (V) having 3 chromophore moieties. The startingmaterial is tri-2-mercapto-ethylamine (TMEA). TMEA is dissolved inwater. 3 moles of Procion™ Yellow MX3R for each mol of TMEA were added(pH 7.5). During all the reaction the pH and temperature were kept atrespectively 7.5 (by addition of Na₂CO₃) and 20° C. The dye was “saltedout” as described previously after the pH stabilized.

Example 12

[0209] This example illustrates the synthesis of a reactive dyeaccording to formula (V). The starting material was1-amino-diethyl-2,2′-bis-isothiouronium chloride. 3 moles of the1-amino-diethyl-2,2′-bis-isothiouronium chloride were dissolved in waterand the pH adjusted to 7.5. Cyanuric chloride (1 mol) dissolved inacetone was added slowly at 5° C., then when no more HCl was produced,the temperature was increased at 40° C. When the pH stabilized again,the temperature was raised to 90° C. The pH is kept at 7.5 during allreaction by addition of Na₂CO₃. In the second stage of the reaction, theisothiouronium moiety was hydrolyzed with dilute NaOH (added to thesolution until pH 10.5 is reached). In the last stage, 6 moles of dye ormixtures of dyes dissolved in acetone were added at 20° C. (the pH iskept at 7.5° C. by addition of Na₂CO₃).

Example 13

[0210] This example illustrates the synthesis of a reactive dyeaccording to formula (VI) from α-β-dibromo-propionamido orα-bromoacrylamide starting dyes. Examples of such starting dyes can bebought from Ciba under the trademark Lamasol™. In this example, 1 mol ofLamasol™ Blue 3R (Ciba) was reacted with 2 moles of cysteamine at 30° C.and at pH 7.5. When the reaction was complete, 2 moles of cyanuricchloride were added while the pH and temperature were kept atrespectively 7.5 by addition of Na₂CO₃ at 10° C.

Example 14

[0211] This example is similar to example 13.2,4,6-trifluoro-5-chloro-pyrimidine was used instead of cyanuricchloride. The other conditions are identical.

Examples 15, 16, 17 and 18

[0212] The following examples illustrate some reactive dye compoundsaccording to formula (VII). The first step of the synthesis consists ofthe substitution or addition on a starting reactive dye of 2 leavinggroups by two cysteamine derivatives. In the second step of thereaction, two activated N-heterocycles are reacted on the amino side ofthe cysteamine derivatives.

Ex. 15

[0213]

Ex. 16

[0214]

Ex. 17

[0215]

Ex. 18

[0216]

[0217] Method of use

[0218] The dye compounds herein are suitable for dyeing and printing awide variety of substrates, such as silk, leather, wool, polyamide,polyester fibers and polyurethanes, keratin fibres such as hair, and inparticular cellulosic materials, such as the natural cellulose fibres,cotton, linen, hemp and the like, paper, and also cellulose itself andregenerated cellulose, and hydroxyl-containing fibres contained in blendfabrics, for example blends of cotton with polyester or polyamidefibres.

[0219] The reactive dye compounds of the present invention can beformulated in various ways, in particular in the form of a solidmixture, aqueous solutions and printing pastes. Thus according to thepresent invention there is provided a dye composition comprising one ormore of the dye compounds described herein together with any carriermaterial suitable for use in a dye composition.

[0220] Preferred dye compositions herein comprise an acidic buffermaterial. Any acidic buffer suitable for use in dye compositions can beused herein. An example of a suitable buffer is a mixed phosphate buffergiving a potential aqueous solution pH of 5-7, preferably 6.5. When thedye composition herein is in the form of a paste a preferred ingredientis a thickening agent. Any suitable thickening agents suitable for usein dye compositions can be used herein.

[0221] In particular the dye compositions can be applied to cellulosicfibers (usually 0.1% to 10% dye on mass of fiber). It is necessary touse alkali in a fixing step to bring about covalent bonding to thecellulosate anion. If applied to polyamides the dye is preferablyapplied at pH 3-6 at the boil.

[0222] When the dye composition is in the form of an aqueous solution oraqueous gel/paste, the dye composition preferably has a pH of about 5 or6.

[0223] When the dye composition is being used for dyeing hair, thecomposition can comprise one or more of the compounds described hereineither alone or in admixture with other well known hair dye compoundssuch as oxidative dyes, direct dyes, and the like.

[0224] The dyeing and printing processes that can be used with the dyesherein are conventional processes which are well known and which havebeen widely described in the technical and patent literature. The dyecompounds herein are suitable for dyeing both by the exhaust method(long liquor) and also by the pad-dyeing method, whereby the goods areimpregnated with aqueous, salt-containing or salt-free dye solutions. Inthe case of cellulosic substrates the dye is fixed after an alkalitreatment or in the presence of alkali, if appropriate with theapplication of heat. The dye compounds herein are also suitable for thecold pad-batch cellulosic fiber-dyeing method, after which the dyetogether with the alkali is applied to cellulosic fabric using thepad-mangle, batched on a roller and then fixed by storage at roomtemperature (usually at 4-24 hours). After fixing, the dyeings or printsare thoroughly rinsed with cold and hot water, if appropriate with theaddition of an agent acting as a dispersant and promoting the diffusionof the non-fixed portions. Thus in accordance with another aspect of thepresent invention there is provided a use of the reactive dyes of thepresent invention for dyeing and printing substrates such as cotton,wool, nylon, silk, keratin, leather, paper and the like. The compoundsherein can be used in methods of dyeing all of the substrates listedabove by applying an aqueous solution of one or more of the reactivedyes of the present invention to the substrate to be dyed under suitableconditions of pH and temperature.

[0225] The following examples serve to illustrate the dyeing of fabricwith the reactive dyes according to the present invention.

Example A

[0226] The dye produced in example 1 was applied to cotton fabric by thestandard long-liquor dyeing process. The dye bath was set with 2% (onweight of fibre or o.w.f.) dye, 40 g/l sodium sulphate and the scouredcotton fabric; the temperature was raised to 50° C. and the fabricagitated in liquor at this temperature for 30 minutes. At this stagesodium carbonate 15 g/l was added and the fabric further agitated foranother 30 minutes. The bath was found to be almost water white i.e. thedyebath exhaustion was >95%.

[0227] The dyed sample was removed from the bath, rinsed in cold waterand soaped off at the boil in an aqueous solution of the nonionicdetergent Sandozin™ NIE (2 parts per 1000); soaping for 15 minutes atthe boil removed hardly any colour. By measuring the concentration ofdye removed by the rinsing and soaping processes the degree of dyefixation could be measured; the Total Covalent Fixative Efficiency (% F)related to the dye originally applied was found to be 93%.

[0228] By way of comparison, an equivalent amount of Procion™ YellowMX-3R was applied to cotton fabric in the presence of 80 g/l sodiumsulphate (this dye showed very poor uptake on cotton or exhaustion if 40g/l salt were to be used).

[0229] The dyeings produced, following fixation with sodium carbonate,rinsing and soaping off, was very weak compared to the dyeing producedwith the dye of example 1 above; when Total Fixation Efficiency (% F)was calculated it was found to be only 38%. The new classes of dyeaccording to the present invention are very efficient in giving veryhigh levels of fixation even when dyeing cellulosic fibers from bathscontaining low salt concentrations (40 g/l sodium sulphate).

Example B

[0230] The reactive dye (3 b) obtained in example 3 was applied tocotton by the method described above. Deep yellow dyeings of TotalFixation Efficiency (% F) greater than 90% were produced.

Example C

[0231] The tri-monochloro-s-triazine dye prepared in example 7 wasapplied to cotton fabric by the following long-liquor dyeing process.

[0232] The dyebath was set with cotton fabric, 80 g dm⁻³ sodiumsulphate, 2% (owf) dye. The bath was raised to 80° C. and dyeingcontinued at this temperature for 30 minutes; sodium carbonate (20 g/l)was added and dyeing continued for a further 30 minutes at 80° C. Thedyed fabric was removed from the exhausted bath, rinsed and soaped-offas described in Example A. A Total Fixation Efficiency of 91% wasobtained.

Example D

[0233] The reactive dye compound (8b) prepared in example 8 was appliedto cotton fabric by the method described above, but in this case only 2%dye (o.w.f.) and 40 g/l sodium sulphate were used. Total FixationEfficiency was measured at 92%.

Example E

[0234] The reactive dye compound prepared in example 11 was applied bylong liquor dyeing to cotton fabric: 3% dye (o.w.f.), 60 g/l Na₂SO₄. Thebath was raised to 80° C. and dyeing continued at this temperature for30 minutes; sodium carbonate (20 g/l) was added and the dyeing continueda further 30 minutes at 80° C. Cold water rinsing and “soaping” at theboil with non-ionic detergent (Sandozine NIE 2 g/l) completes theprocess. Excellent color with deep shade was obtained. The TotalFixation Efficiency was 90%.

1. A reactive dye compound comprising at least one chromophoric moiety Dand at least one leaving group Y wherein the sum of the number ofchromophoric moiety or moieties D and the number of leaving group orgroups Y is at least equal to 5, preferably in the range of from 5 to12, more preferably from 5 to
 6. 2. A reactive dye compound according toclaim 1 wherein the reactive dye compounds comprises at least twoasymmetric bridging moieties, preferably at least two dissymmetricbridging moieties.
 3. A reactive dye according to claim 2 wherein thebridging moieties are selected from the group consisting of cysteamine,cysteine and derivatives thereof, even more preferably from the groupconsisting of cysteamine and cysteine.
 4. A reactive dye compound havingthe formula (I) below:

wherein D is a chromophore; L is a linking moiety, preferably selectedfrom the group consisting of —NR—, —C(O)NR—, —NRSO₂—, —(CH₂)_(k)— and—SO₂—(CH₂)_(k)— wherein R is H or C₁-C₄ alkyl which can be substitutedby halogen, preferably fluorine or chlorine, hydroxyl, cyano, C₁-C₄alkoxy, C₂-C₅ alkoxycarbonyl, carboxyl, sulfamoyl, sulfo or sulfato andwherein k is an integer with a value between 1 and 4: Z is any moietyforming at least three covalent bonds with other moieties, preferablyselected from the group consisting of nitrogen (N),

 and aromatic compounds, more preferably from the group consisting ofaromatic compounds activated by electron withdrawing groups andN-heterocycles, even more preferably from the group consisting oftriazine, pyrimidine, quinoxaline, pyrimidinone, phthalazine,pyridazone, pyrazine and

 still more preferably from the group consisting of triazine,pyrimidine, and quinoxaline, still even more preferably from triazine; Yis any leaving group, preferably selected from the group consisting of—Cl, —Br, —F, —I, —SO₃H, —OSO₃H, —SSO₃H, —O—C₆H₄—SO₃H, —OCO—CH₃,—OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄ alkyl, —OSO₂—N(C₁-C₄ alkyl)₂,

 and quaternized nitrogen derivatives, more preferably selected from thegroup consisting of —Cl, —Br, —F and —OSO₃H, even more preferably fromthe group consisting of —F and —Cl when Y is bonded to an N-containingheterocycle and —Br when Y is bonded to

G1 is selected from the group consisting of Y and —B-G2; G2 is selectedfrom the group consisting of

B is a bridging moiety selected from the group consisting of —S—

and —S—CR′₂—CR′₂— wherein R′ is selected from the group consisting of H,C1-C10 alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H;and wherein R″ is selected from the group consisting of H, C1-C4 alkylgroup and —CR′₂—CR′₂—S-G2. B preferably being —NH—CH₂—CH₂—S— or —NH—CHCOOH—CH₂—S—; wherein there is more than one D, R, R′, R″, L, Z, Y,G1, G2 or B these are not necessarily the same; and wherein the reactivedye compound comprises at least one group G2; and salts and estersthereof.
 5. A reactive dye compound according to claim 4 having theformula (II):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; B is

wherein R′ is selected from the group consisting of H, C1-C10 alkylgroup, C1-C10 carboxylic acid and sulphonate, preferably H; and R″ isselected from the group consisting of H, C1-C4 alkyl group, B preferablybeing —NH CH₂—CH₂—S— or —NH—CHCOOH—CH₂—S—; wherein when there is morethan one D, L, Z, Y, R, R′, R″ or B group these are not necessarily thesame; and salts and esters thereof.
 6. A reactive dye compound accordingto claim 4 having the formula (III):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; G1 is as defined inclaim 4; G2 is as defined in claim 4; B is

wherein R′ is selected from the group consisting of H, C1-C10 alkylgroup, C1-C10 carboxylic acid and sulphonate, preferably H; and R″ isselected from the group consisting of H and C1-C4 alkyl group, Bpreferably being —NH —CH₂—CH₂—S— or —NH —CHCOOH—CH₂—S—; wherein whenthere is more than one D, R, R′, R″, L, Z, Y, G1, G2 or B group theseare not necessarily the same; and wherein the reactive dye compoundcomprises at least one group G2; and salts and esters thereof.
 7. Areactive dye compound according to claim 4 having the formula (IV):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; G1 is as defined inclaim 4; G2 is as defined in claim 4; B is as defined in claim 4;wherein at least one, and preferably all, B is —S—, wherein when thereis more than one B, D, R, L, Z, Y, G1 or G2 within the same moleculethese are not necessarily the same; and wherein the reactive dyecompound comprises at least one group G2; and salts and esters thereof.8. A reactive dye compound according to claim 4 having the formula (V):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; G1 is as defined inclaim 4; G2 is as defined in claim 4; B is a bridging group selectedfrom the group consisting of

and —S —CR′₂—CR′₂—; wherein R″ is selected from the group consisting ofH, C1—C4 alkyl group and CR′₂—CR′₂—S— G2; and wherein R′ is selectedfrom the group consisting of H, C₁-C₁₀ alkyl group, C1-C10 carboxylicacid and sulphonate, preferably H, wherein when there is more than oneD, R, R′, R″, L, Z, Y, G1, G2, or B group they are not necessarily thesame; and wherein the reactive dye compound comprises at least onebridging group B wherein R″ is —CR′₂—CR′₂—S-G2; and salts and estersthereof.
 9. A reactive dye compound according to claim 4 having theformula (VI):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; G1 is as defined inclaim 4; G2 is as defined in claim 4; B is a bridging moiety, preferablyselected from the group consisting of —S—,

and —S—CR′₂—CR′₂— wherein R″ is selected from the group consisting of H,C1-C4 alkyl group and —CR′₂—CR′₂—S-G2 wherein R′ is selected from thegroup consisting of H, C1-C₁₀ alkyl group, C1-C₁₀ carboxylic acid andsulphonate, preferably H, B preferably being —NH—CH₂—CH₂—S— or—NH—CHCOOH—CH₂—S—; wherein when there is more than one D, R, R!, R′, L,Z, Y, G1, G2 or B group they are not necessarily the same; and salts andesters thereof.
 10. A reactive dye compound according to claim 1 havingthe formula (VII):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; B is selected from thegroup consisting of

wherein R″ is selected from the group consisting of H and C1-C4 alkylgroup; and wherein R′ is selected from the group consisting of H, C1-C10alkyl group, C1-C10 carboxylic acid and sulphonate, preferably H; Bpreferably being —NH—CH₂—CH₂—S— or —NH —CHCOOH—CH₂—S—; wherein each ofR, R′, R″, L, Z, Y and B are not necessarily the same; and salts andesters thereof.
 11. A reactive dye compound according to claim 1 havingthe formula (VIII):

wherein D is as defined in claim 4; L is as defined in claim 4; Z is asdefined in claim 4; Y is as defined in claim 4; R is selected from thegroup consisting of H, C₁-C₁₀ alkyl group, C1-C₁₀ carboxylic acid andsulphonate, preferably H and COOH, more preferably H; wherein each of D,R, Z and Y within are not necessarily the same; and salts and estersthereof.
 12. A reactive dye compound according to claim 1 having theformula (IX):

wherein D is as defined in claim 4; Z is as defined in claim 4; Y is asdefined in claim 4; R is selected from the group consisting of H, C1-C₁₀alkyl group, C1-C₁₀ carboxylic acid and sulphonate, preferably H andCOOH, more preferably H; wherein each of Z or Y are not necessarily thesame; and salts and esters thereof.
 13. A method for synthesizing areactive dye compound according to claim 1 using a starting reactive dyecompound and bridging moiety B as defined in claim 4, wherein saidmethod comprises the steps of: a) reacting said starting dye compoundwith said bridging group B and forming one bond, and b) reacting thesecond moiety of said bridging group B with a moiety Z as defined inclaim
 4. 14. A method according to claim 13, wherein said bridgingmoiety B is dissymmetric.
 15. A method according to claim 14, whereinsaid bridging moiety B has the following formula:

wherein R′ is selected from the group consisting of H, C₁-C₁₀ alkylgroup, C₁-C₁₀ carboxylic acid and sulphonate, preferably H; and R″ isselected from the group consisting of H and C1-C4 alkyl group.
 16. Amethod according to claim 15, wherein at least one R′ is COOH.
 17. Amethod according to claims 13 to 16 wherein step a) and/or step b) isrepeated at least two times.
 18. A method for dyeing a substrate whereinsaid method comprises the step of applying a composition comprising areactive dye compound according to any of claims 1 to 12.